Spectrally sensitized silver halide photographic emulsion

ABSTRACT

A silver halide photographic emulsion which is spectrally sensitized so that it has a maximum sensitivity wave length within the region of 580 nm - 640 nm, characterized by containing in a super sensitizing amount the combination of at least one carbocyanine dye represented by the general formula (I) and at least one of the dyes selected from the group consisting of dyes represented by the general formula (II) and (III):   WHEREIN Z1 represents the grouping necessary for the formation of Beta -naphthothiazole or Beta -naphthoselenazole ring, Z2 represents the grouping necessary for the formation of benzoxazole ring, A1 represents a hydrogen atom, an alkyl radical or an aryl radical, R1 and R2 each represents an alkyl radical, at least one of which represents a hydroxyalkyl radical, a carboxyalkyl radical or alkyl radical having a sulfo group, X1 represents an acid anion group, and l is 1, or 2 the dye forming an intramolecular salt when l is 1:   WHEREIN Z3 and Z4 each represents the grouping necessary for the formation of a benzothiazole, benzoselenazole, Beta naphthothiazole or Beta -naphthoselenazole ring, A2 represents a hydrogen atom, an alkyl radical having less than three carbon atoms or an aryl radical, R3 and R4 each represents an alkyl radical, at least one of which represents a hydroxyalkyl radical, a carboxyalkyl radical or an alkyl radical having a sulfo group, X2 represents an acid anion group, and m is 1 or 2, the dye forming an intramolecular salt when m is 1.   WHEREIN Z5 represents the grouping necessary for the formation of a benzoxazole orbenzimidazole ring, Z6 represents the grouping necessary for the formation of a benzothiazole, benzoselenazole or Beta -naphthothiazole ring, A3 represents a hydrogen atom, an alkyl radical having less than three carbon atoms or an aryl radical, R5 and R6 each represents an alkyl radical, at least one of which represents a hydroxyalkyl radical, a carboxyalkyl radical or an alkyl radical having a sulfo group, X3 represents an acid anion group, and n is 1, the dye forming an intramolecular salt when n is 1.

United States Patent 1 1 Shiba ct a1.

1 1 Nov. 25. 1975 1 1 SPECTRALLY SENSITIZED SlLVER HALIDE PHOTOGRAPH":EMULSION (751 Inventors: Keisuke Shiba; Akira Sato. both ofKanagawa.]apan Fuji Photo Film Co.. Ltd.. Minami-ashigara. Japan [22Filed: July 20. 1973 21 Appl. No: 381,137

[731 Assignee:

Primary Examiner1 Travis Brown Attorney, Agent. or Firm-Sughrue.Rothwell. Mion, Zinn & Macpeak [57] ABSTRACT A silver halidephotographic emulsion which is spectrally sensitized so that it has amaximum sensitivity wave length within the region of 580 nm 640 nm.characterized by containing in a super sensitizing amount thecombination of at least one carbocyanine dye represented by the generalformula (1) and at least one of the dyes selected from the groupconsisting of dyes represented by the general formula (11) and (111):

wherein Z, represents the grouping necessary for the formation ofB-naphthothiazole or B-naphthoselenazole ring. Z represents the groupingnecessary for the formation of henzoxazole ring. A represents a hydrogenatom. an alkyl radical or an aryl radical. R and R each represents analkyl radical. at least one o1 which represents a hydroxyalkyl radical.a carbosyalkyl radical or alkyl radical having a sull'o group X.represents an acid anion group. and l is l. or Z the dye forming anintramolecular salt when l is l:

wherein Z and Z each represents the grouping necessary for the formationof a benzothiazole. benzosclen azole, B-naphthothiazole orB-naphthoselenazolc ring. A; represents a hydrogen atom. an alkylradical having less than three carbon atoms or an aryl radical. R and Reach represents an alkyl radical. at least one oi which represents ahydroxyalkyl radical. a carbosyal kyl radical or an alkyl radical havinga sulto group. X;- represents an acid anion group. and m is l or Z. thedye forming an intramolccular salt when m is l wherein Z represents thegrouping necessary for the formation of a benzoxazole orbenzimidazolering. Z represents the grouping necessary for the formation of abenzothiazole, benzoselenazole or B-naphthothiazole ring, A represents ahydrogen atom. an alkyl radical having less than three carbon atoms oran aryl radical. R and R each represents an alkyl radical. at least oneof which represents a hydroxyalkyl radical. a carboxyalkyl radical or analkyl radical having a sulfo group. X, represents an acid anion group.and n is l. the dye forming an intramolecular salt when n is 1.

(Xi n 9 Claims. 17 Drawing Figures US. Patent Nov. 25, 1975 Sheet 1 of 33,922,170

m fix 9 8 H04 0X 5 fill WAVELENGTH [mp] U.S. Patent Nov. 25, 1975Sheet2of3 3,922,170

FIG 9 FIG. IO

FIG. II

FIG. l2

FIG. l3

FIG. I4

FIG. I5

WAVELENGTH (my) SP-I HO I6 WAVELENGTH (nm FIG. I?

WAVELENGTH nm SPECTRALLY SENSITIZEI) SILVER HALIDE PHOTOGRAPI-IICEMULSION BACKGROUND OF THE INVENTION 1. Field of the Invention Thepresent invention relates to a silver halide photographic emulsion inwhich a specific wave length range is highly spectrally sensitized by asupersensitization, more especially, the present invention relates to asliver halide photographic emulsion in which the wave length range from580 nm to 640 nm is spectrally sensitized,

2. Description of the Prior Art An appropriate spectral sensitivitydistribution over the visible wave length range to which human eyes aresensitive is given to conventional photographic sensitive materials. Anappropriate spectral sensitivity distribution is required for suitablecolor reproduction. Usua ally, a combination of two or more sensitizingdyes is selected, the combination having a supersensitization effect.

To obtain excellent color reproduction, it is not preferred to have highsensitivity at too long a wave length, eg a wave length longer than 660nm (the wave length at the maximum sensitization) or to have highsensitivity only at too short a wave length region, e.g., shorter than580 nm (the wave length at the maximum sensiti zation). It is difficultto selectively increase sensitivity within the wave length region from580 nm to 640 nm, and the solution to this problem is an importantmatter in this technical field.

SUMMARY OF THE INVENTION Accordingly, a first object of the presentinvention is to provide a new supersensitization technique toselectively increase the sensitivity within the wave length region fromabout 580 nm to 640 nm.

Another object of the present invention is to diminish the color residuewhich typically remains after development.

Moreover, a further object of the present invention is to provide asensitizing dye that does not diffuse into and sensitize adjacentsensitive layers when a layer ofa multi layer sensitive material isselectively spectrally sensitized.

The above objects are attained as follows:

To a photographic emulsion there is added the combination of at leastone carbocyanine dye of general formula (I) and at least one dyeselected from the group consisting of dyes of general formula (II) anddyes of general formula (III), in an amount sufficient to provide asupersensitization:

wherein Z represents the grouping necessary for the formation of aB-naphthothiazole or B-naphthoselenazole ring, Z represents the groupingnecessary for the formation of a benzoxazole ring, A, representshydrogen atom, an alkyl group, (e.g., an unsubstituted alkyl grouphaving up to 4 carbon atoms or a monoaralkyl group wherein the alkylmoiety has up to 2 4 carbon atoms) or monoaryl (ie. unsubstituted or substituted monoaryl) radical, R and R each represents an alkyl (i.e. anunsubstituted alkyl group preferably having up to 8 carbon atoms and asubstituted alkyl group wherein the alkyl moiety preferably has up to 4carbon atoms) radical, at least one of which is hydroxyalkyl,carboxyalkyl or an alkyl radical having a sulfo group, X is an acidanion group, and I is l or 2, being 0 1 when the dye forms anintramolecular salt (similar to a betaine structure wherein Z;, and Z,each represents the grouping necessary for the formation of abenzothiazole, benzoselenazole, B-naphthothiazole or B-naphthoselenuzolering. A represents a hydrogen atom. an alkyl radical having less thanthree carbon atoms or a monoaryl radical (i.e., unsubstituted orsubstituted monoaryl R and R each represents an alkyl (ie anunsubstituted alkyl group preferably having up to 8 carbon atoms and asubstituted alkyl group wherein the alkyl moiety preferably has up to 4carbon atoms) radical. at least one of which is a hydroxyalkyl,carboxyalkyl or alkyl radical having a sulfo group, X-{ is an acid aniongroup. and m is 1 or 2, being l when the dye forms an intramolecularsalt (similar to a betaine structure).

wherein Z represents the grouping necessary for the formation of abenzoxazole or benzimidazole ring, Z represents the grouping necessaryfor the formation of a benzothiazole, benzoselenazole orB-naphthothiazole ring, A represents a hydrogen atom, an alkyl group(e.g. an unsubstituted alkyl group having up to 4 carbon atoms and amonoaralkyl group wherein the alkyl moiety has up to 4 carbon atoms) ora monoaryl (i.e. unsubstituted or substituted monoaryl) radical. R and Reach represents an alkyl (ie. an unsubstituted alkyl group preferablyhaving up to 8 carbon atoms and a substituted alkyl group wherein thealkyl moiety prefer ably has up to 4 carbon atoms) radical, at least oneof which is hydroxyalkyl, carboxyalkyl or an alkyl radical having asulfo group, X represents an acid anion group, and n is l or 2, being Iwhen the dye forms an intramolecular salt (similar to a betainestructure) BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWINGS FIGS. 1 15 arecharacteristic curves of dyes employed as described in the Examplesgiven hereafter.

FIG. 16 is the spectral transmittance curve of an SP- l-filter and FIG.I7 shows the spectral transmittance of filters SC-SO & SC56.

Atom 1. bawimm- AMWJ, 1 mun-Mr gmup Ivy 1! 1: E mp 11 HUTNAHQ w imlu MUgn/Jp m 511mm minim! Mun/Wm;

mini. Lh uinn F 3 hulk MI mm hum Arr Uwumnni} Hand m gyunwn .iyL xiiiwig and the Ii'm Whiiu WIN! mmwgun u Mammy lwwwc' 3w mud mm W mud m :a

\ flllDl Control Sensitizing Dyes:

(R) s c H o C-CH-C -CHC i Br e C H i l 5 O G-CH=C-CH==C\ l N/ N I c-CH==GCH==C i Cl l The silver halide photographic emulsion used in thisa conventional manner, for example, gold sensitized invention can bemanufactured by any common man- (US. Pat. Nos. 2,540,085, 2,597,856,2,597,9l5, ner. e.g., precipitated by the single or double jet2,399,083, etc), Group VIII metal ion sensitized, sul

method or a combination thereof, and contains aged fur sensitized (US.Pat. Nos. l,574,944. 2,278,947, silver chloride, bromide, iodide ormixed silver halide 55 2,440,206, 2,l40.689, 3,189,458, 3,415,649, etc),re-

particles. The preferred silver halides are silver iododuCIiOnsensitized N 2. l bromide (A preferred halogen composition by mole 7r2,419,974. 2,983,6[0 etc.) or sensitized by a combinaof iodine is nogreater than l0 mol "/c, for example, tion of the methods mentionedabove. from 2 to 7 mol "1? iodine.) or chloroidobromide (A Thephotographic emulsion according to this inven preferred halogencomposition by mo] 92 ofiodine is no 60 tion may contain as a chemicalsensitizer a sulfur sensigreater than 5 mol /2. for example, from 2 to 3m 7 tizer such as allyl thiocarbamide, thiourea,sodium thioiodine. Thebromine or chlorine composition is up sulfate and cysteine; a noblemetal sensitizer such as tional. The average diameter of the silverhalide partipotassium chloroaurate, aurous thiosulfate and potascles isnot limited but preferably is 0.04 2 (arithmetisium chloropalladate; areducing sensitizer such as tin cal mean determined by, for example, theproje t d chloridephenyl hydrazine and reductone,and the like. areamethod). It may contain other sensitizers such as polyoxyethyl- Thesilver halide photographic emulsion used in this fine COmPOUIIdS h H5"1056 diSClOSed i HI- N invention can be physically and chemicallysensitized in 2,716,062, polyoxypropylene compounds and compounds havingquaternary ammomium group such as those disclosed in U.S. Pat. Nos.2,271,623; 2,334,864; 2,288,226 and the like. Further, the photographicemulsion may contain anti-fogging agents such as nitrobenzimidazole andammonium chloroplatinate and stabilizers such as 4-hydroxy-6-methyl-l,3,3a,7-tetrazaindene. The photographic emulsion may also containhardening agents such as formaldehyde. chrome alum,l-hydroxy-3,S-dichlorotriazine soda, glyoxal and dichloroacrolein; andcoating assistants such as saponin and sodium alkylbenzene sulfonates.

When the silver halide emulsion used in this invention is used for acolor light-sensitive material, it may contain color couplers anddispersing agents therefor. Among the color couplers, especially cyancoupler are present. For example, couplers of the phenol series asdescribed in U.S. Pat. No. 2,698,794 or couplers of the naphthol seriesare described in U.S. Pat. No. 2,474,293 are especially useful.

The silver halide photographic emulsion used in this invention can bebased upon protective colloids other than gelatin, for example, gelatinderivatives such as phthalated or malonated gelatin; cellulosederivatives such as hydroxyethyl or carboxymethyl cellulose; solublestarches such as dextrin; hydrophilic polymers such as polyvinylalcohol, polyvinyl pyrrolidone, polyacryiamide and polystyrene sulfonicacid; plasticizers for dimensional stability; latex polymers and mattingagents. The generally used ratio by weight of silver halide to thebinder is from about 1:4 to 4:1.

The finished emulsion is coated on any suitable support, for example,baryta paper, resin-coated paper, synthetic paper, triacetate film,polyethylene terephthalate film, glass plate and other plastic bases.

The sensitizing dyes used in this invention can be added to the emulsionas a solution in water or a watermiscible organic solvent such asmethanol, ethanol, methyl cellosolve, pyridine and the like.

The amount of the dyes added is as is commonly used for thesupersensitization, e.g. about 55 X l X 10 mol of dye per mol of silver,and the ratio of the dye or dyes of general formula (11) and/or (III) tothe dye or dyes of the general formula (I) is preferably about 1:100-121(mol ratio). It is especially preferred that the amount of dye or dyesof general formula (1) be larger than that of the dye of general formula(11) (mol ratio).

The dyes used in this invention can be used for spectral sensitizationaccording to the method described in German Laid Open Specification2,104,283 and in U.S. Pat. No. 3,649,286.

Specific examples according to this invention are described below, butthis invention is not restricted only to the examples. Unless otherwiseindicated all parts and percents are by weight.

EXAMPLE 1 Silver halide particles were precipitated in a gelatin binderby the double jet method, physically aged in a common manner, subjectedto desalting treatment and chemically aged with 4 ml of an aqueoussolution con taining hypo and having a concentration of l by weight and10 ml ofan aqueous solution containing potassium chloroaurate and havinga concentration of 1 71 by weight so that a silver iodobromide (iodinecontent: 6 mol7r) emulsion was manufactured. The emulsion contained 0.6mol of silver halide/kg of emulsion. The grain size of the silver halideformed was 0.8a. One kg of emulsion was placed in a crucible anddissolved in a constant temperature bath at 50C.

A given amount of each sensitizing dye of this inven tion, which wasused for the comparison with the sensitizing dyes according to thisinvention was added to the resulting emulsion as a metlianolic solutionand stirred at 40C. On the other hand, a given amount of each dye forcomparison was added to the resulting emulsion in the same way asdescribed above. 10 cc of an aqueous 0:1 wt.% solution of4-hydroxy-6-methyl-l,3,3a,7-tetrazaindene, 10 cc of a l wtfi? aqueoussolution of lhydroxy-3,S-dichlorotriazine soda and 10 cc of a l wt.%aqueous solution of sodium dodecyl benzene sulfonate were added theretoand the system stirred.

The resulting finished emulsion was coated on a cellulose triacetatefilm base to a dried film thickness of 5 microns, and dried to yield asample of a sensitive ma terial.

The film sample was cut into strips. One strip was ex posed with anoptical wedge to a light source provided with a blue filter (SP 1 ayellow filter (SC-50 and a red filter (SC-56) (all by Fuji Photo FilmCo., Ltd.) using a sensitometer having a 5,400K color tempera ture lightsource. The remaining strips were exposed to obtain spectrograms using adiffraction grating spectrograph having a 2,666K tungsten light source.

The exposed strips were developed with a liquid developer having thefollowing composition at 20C for 2 minutes, stopped, fixed and washedwith water to yield strips having a black-and-white image. The densitiesof these strips were determined by an S-type densitometer (Fuji PhotoFilm Co., Ltd.) to measure the blue filter sensitivity (Sb), the yellowfilter sensitivity (Sy), the red filter sensitivity (Sr) and fog. Thebase value of optical density for determining sensitivity was (fog0.20).

Composition of Liquid Developer:

Water 500 cc Metol Anhydrous Sodium Sulfite 9 Hydroquinone SodiumCarbonate Monohydrate 5 Potassium Bromide Water (to make) The resultsobtained are shown as relative values in Table l. Runs 12 and 13 werecarried out for comparison.

The spectral transmittance curve of the SP-l filter is shown in FIG. 16and those of the SC-SO and SC56 filters in FIG. 17. The resultingspectrograms are shown in FIG. 145.

From the values in Table l and the spectrograms, it can be seen that thecombinations of dyes having a supersensitizing effect according to thisinvention have an excellent effect.

Table l Amount of Amount of S) Sr Sb No dye usedIKg dye used/Kg(Relative IRcIatlu: IRclativc Fug Spcctrugram Ll'llulslult emulsion\uluc) value) \aluc) x H) mull l lll "mull l I IA) I 005 2 I55 96 960.07 4 I00 I00 85 0.08 FIG. I Curve 1 III A) I 32 40 I00 0.06 2 38 50I00 006 FIG. I Z 4 71 65 I00 0.0K IIA) 4 III A) l I I26 85 0.08

4 2 II. I51 III ().II FIG. I 3 4 4 I00 H2 76 0.II 2 III C) I 32 85 0.06

2 32 79 85 0.06 FIG 2 4 IIA) 4 (IIC) l I05 IIO 96 0.09

4 2 I05 H2 96 0.10 FIG. 2 5 3 III E) 2 B5 85 85 0.08

4 I I40 76 009 FIG. 3 6 IIA) 4 lIIE) 2 I56 I56 89 (H0 4 4 I56 I78 780.I0 FIG. 3 7 (II F) I 43 40 86 007 FIG. 4 8 4 1m 4 (II F) 0.5 I00 I1994 um 4 I I00 I26 94 0.08 FIG. 4 9 5 (III A) I 63 67 80 0.08

2 II2 H4 85 0.08 FIG. 5 I0 (IA) 4 (IIIA) I II7 II7 76 0.10

4 2 I58 I66 63 0.1) FIG.5 II 6 III I) 2 56 63 I00 0.07

4 76 80 I00 0.07 FIGv 6 I2 (IA) 4 (III) 2 I40 I58 88 0.08 FIG.6 l3

4 4 I58 I78 85 0.08 7 (1B) 2 I4l H2 96 0.06

4 I60 I32 91 0.07 FIG. 7 Curve l4 8 I60 I28 60 0.07 A (II G) I I00 I25I00 006 2 I25 I32 I00 006 FIG. 7 l5 (IB) 4 (ll G) I 232 200 96 0.07

4 2 232 224 92 007 FIG. 7 I6 Ii (III B] I 63 25 I05 006 2 I00 I00 0.06FIG. 8 I7 IIB) 4 (III B) I 234 200 93 0.06

4 2 250 200 93 0.07 FIG. 8 I8 9 (IC) 2 I4I I26 87 0.07

4 I48 I50 77 0.08 FIG. 9 I9 8 I48 I53 66 0.08 (III C) I I26 II7 96 0.062 I50 I25 80 007 FIG. 9 20 (IC) 4 (IIIC) I 2l4 I58 89 0.08

4 2 250 I58 85 0.08 FIG. 9 2| I0 IIG) '2 I52 I50 87 0.08

4 I52 I52 80 0.08 FIG. I0 22 (II E) I 83 79 96 0.06 2 I00 I00 96 0.07FIG. I0 23 (IG) 4 I 234 200 96 0.07

4 2 234 224 93 0.08 FIG. I0 24 II (IE) 2 I09 76 85 0.08

4 I10 96 76 0.08 FIG. II 25 III B) I 66 62 I00 0.08 2 80 78 88 009 FIG.II 26 (IE) 4 (III!) I I00 I42 50 012 FIG. II 27' 4 2 III I66 35 0.12

' Value too low to be measured The combinations of sensitizing dyeshaving a supersensitization effect according to this invention areuseful for the spectral sensitization of silver halide emulsions in thered sensitive layer of color sensitive material such as color negativeand reversal sensitive materials, the spectral sensitization of silverhalide emulsions used for black-and-white sensitive materials, thespectral sensitization of silver halides used as a printing platesensitive material and the spectral sensitization of 50 cording to thisinvention in order to render practically the green sensitivity less thanthe red sensitivity obtained by this invention. For the formation ofsuch filter layer, dyes are used are described in Japanese PatentPublications Nos. 18459/66, 3504/68. I3l68/68 and 22069164; JapanesePat. applications Nos. 98474/71, 42668/7] and 42667]? I and US. Pat.Nos. 3,440,051,

3,573,289, 3,560,214, 3,615,432 and 3,282,699; Brit- I ish Pat. No.506.385 etc. Especially, dyes which absorb selectively the short waveregion less than 570 nm are useful. The methods are used, which aredescribed in the German Laid-Open Specification No. 2,008,882; U.S. Pat.3,425,834 and 3,282,699; Belgian Pat. Nos. 682,4 I 3, 685,292, 703,939and 627,308; Japanese Pat. Publication Nos. 2l766/68, 13498/68, 15896760and 10254/68 etc. These may be used for the prevention of irradiationand halation.

Practicularly preferred embodiments according to this invention are asfollows:

1. A compound of the formula (I) wherein the heterocyclic ring formed bythe group 2, is the B-naphthothiazole ring, the heterocyclic ring formedby the group Z is a benzoxazole ring, which is substituted at the5-position by a chlorine atom, a trifluoromethyl, methyl or phenylradical and A, is an ethyl radical.

2. A compound of the formula (ll) wherein A is a methyl or ethylradical, R and R, each is a methyl, ethyl, propyl, ally], carboxyalkylor sulfoalkyl radical.

3. A compound of the formula (III) wherein A is a hydrogen atom, amethyl or ethyl radical, R and R each is a methyl, ethyl, propyl, allyl,carboxyalkyl or sulfoalkyl radical. A color sensitive materialcomprising an emulsion containing a cyan coupler, characterized bycontaining in a supersensitizing amount the combination of at least onecarbocyanine dye represented by general formula (I) and at least one dyeselected from the group consisting of dyes represented by generalformula (II) and (11]).

While the invention has been described in detail and with reference tospecific embodiments thereof, it will be apparent to one skilled in theart that various changes and modifications can be made therein withoutdeparting from the spirit and scope thereof.

What is claimed is:

l. A silver halide photographic emulsion which is spectrally sensitizedso that it has a maximum sensitiv ity wave length within the region of580 nm 640 nm, characterized by containing in a supersensitizing amountthe combination of:

at least one carbocyanine dye represented by general formula (I) and atleast one dye represented by general formula (III):

wherein Z, represents the grouping necessary for the formation ofB-naphthothiazole or B-naphthoselenazole ring, Z, represents thegrouping necessary for the formation of benzoxazole ring, A, representsa hydrogen atom, an alkyl radical, or an aryl radical, R, and R eachrepresents an alkyl radical, at least one of which represents ahydroxyalkyl radical, a carboxyalkyl radical or alkyl radical having asulfo group,

x, represents an acid anion group, and 1 is l or 2, the dye forming anintramolecular salt when I is l:

wherein Z represents the grouping necessary for the formation of abenzoxazole or benzimidazole ring, 2,, represents the grouping necessaryfor the formation of a benzothiazole, benzosclenazole orB-naphthothiazole ring, when 2,, is a benzimidazole ring and 2,,represents the grouping necessary for the formation of a bcnzothi azoleor benzoselenazole ring when Z is a benzoxazole ring, A, represents ahydrogen atom. an alkyl radical having less than three carbon atoms oran aryl radical. R and R each represents an alkyl radical, at least oneof which represents a hydroxyalkyl radical. a carboxyalkyl radical or analkyl radical having a sulfo group, X represents an acid anion group,and n is l, the dye forming an mtramolecular salt when n is l,

2. The silver halide photographic emulsion of claim 1, wherein thehetero ring firmed by Z Z and Z,- is substituted with at least onesubstituent. said substituent being selected from the group consistingof an alkyl group, a halogen atom, a monoaryl group, an alkoxy group, ahydroxy group, an alkoxy carbonyl group, a cyano group, an amino group,an aminocarbonyl group, a monoaryloxy group and an acyl group.

3. The silver halide photographic emulsion of claim 1, wherein Z is abenzoxazole. S-methyl benzoxazole, 5,6-dimethyl benzoxazole,Schlorobenzoxazole. 5- chloro-o-methyl benzoxazole, S-bromobenzoxazole.S-phenyl benzoxazole, S-tolyl benzoxazole. S-methoxy benzoxazole,S-hydroxy benzoxazole, S-methoxycarbonyl benzoxazole, S-ethoxycarbonylbenzoxazole, S-trifluoromethyl benzoxazole. S-cyanobenzoxazole, 5-aminobenzoxazole, 5-phenoxybenzoxazole. or S-acetyl benzoxazole ring;wherein A,, and A each is a hydrogen atom, a methyl, ethyl. propyl.phenethyl or phenyl radical; wherein R,, R R and R each is a methyl.ethyl, propyl, allyl, 2-carboxyethyl. 4-carboxybutyl, 3- carboxypropyl,Z-methoxyethyl, 3-sulfopropyl, 3-sulfobutyl,2-(3-sulfopropoxy)ethyl,2-hydroxy-3-sulfo' propyl, 3-sulfopropoxyethoxyethyl, Z-bromoethyl. orp-sulfophenethyl;

Z is a ring as described for Z or 5-chlorobenzimidazole,5,-dichlorobenzimidazole. S-trifluoromethylbenzimidazole,S-methoxycarbonyl benzimidazole or 5-cyano-6-chlorobenzimidazole ring;and X,, and X each represents an iodine, bromine, chlorine, p-toluenesulfonic acid, benzene sulfonic acid, ethyl sulfate, perchlorate, orrhodan ions.

4. The silver halide photographic emulsion of claim I, wherein said dyeof the general formula (I) is Se CH l l c P- N/ (2H5 llllC) (lllDl 5.The silver halide photographic emulsion of claim 1, wherein said dyes ofthe general formula (I), and (III) are present at a level of from about5 X to l X 10 mol of dye per mol of silver and wherein the molar ratioof the amount of dye of the general formula (ll) and (III) to the amountof dye of the general formula (l) is about l:100 to lzl.

6. The silver halide photographic emulsion of claim 1, wherein Z is a,B-naphthothiazole ring Z is a benz oxazole ring which is substituted atthe 5-position with a chlorine atom. a trifluoromethyl group, a methylgroup or a phenyl group and A is an ethyl group.

c14 )3 Sc? 7. The silver halide photographic emulsion of Llilllll 1,wherein A is a hydrogen atom a methyl group, or an ethyl group, R and Reach is a methyl group. an ethyl group, a propyl group, an ally] group.a carhoxynlkyl group or a sulfoalkyl group.

8. The silver halide photographic emulsion of claim 1, wherein saidemulsion additionally contains phenol or naphol series cyan coupler,

9. A silver halide photographic material comprising a support havingthereon the silver halide emulsion ol claim I.

1. A SILVER HALIDE PHOTOGRAPHIC EMULSION WHICH IS SPECTRALLY SENSITIZEDSO THAT IT HAS A MAXIMUM SENSITIVITY WAVE LENGTH WITHIN THE REGION OF580 NM - 64O NM, CHARACTERIZED BY CONTAINING IN A SUSPERSENSITIZINGAMOUNT THE COMBINATION OF: AT LEAST ONECARBOCYANINE DYE REPRESENTED BYGENERAL FORMULA (I) AND AT LEAST ONE DYE REPRESENT BY GENERAL FORMULA(III):
 2. The silver halide photographic emulsion of claim 1, whereinthe hetero ring formed by Z2, Z5 and Z6 is substituted with at least onesubstituent, said substituent being selected from the group consistingof an alkyl group, a halogen atom, a monoaryl group, an alkoxy group, ahydroxy group, an alkoxy carbonyl group, a cyano group, an amino group,an aminocarbonyl group, a monoaryloxy group and an acyl group.
 3. Thesilver halide photographic emulsion of claim 1, wherein Z2 is abenzoxazole, 5-methyl benzoxazole, 5,6-dimethyl benzoxazole,5-chlorobenzoxazole, 5-chloro-6-methyl benzoxazole, 5-bromobenzoxazole,5-phenyl benzoxazole, 5-tolyl benzoxazole, 5-methoxy benzoxazole,5-hydroxy benzoxazole, 5-methoxycarbonyl benzoxazole, 5-ethoxycarbonylbenzoxazole, 5-trifluoromethyl benzoxazole, 5-cyanobenzoxazole,5-aminobenzoxazole, 5-phenoxybenzoxazole, or 5-acetyl benzoxazole ring;wherein A1, and A3 each is a hydrogen atom, a methyl, ethyl, propyl,phenethyl or phenyl radical; wherein R1, R2, R5 and R6 each is a methyl,ethyl, propyl, allyl, 2-carboxyethyl, 4-carboxybutyl, 3-carboxypropyl,2-methoxyethyl, 3-sulfopropyl, 3-sulfobutyl,2-(3-sulfopropoxy)ethyl,2-hydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl, 2-bromoethyl, orp-sulfophenethyl; Z5 is a ring as described for Z2, or5-chlorobenzimidazole, 5,6-dichlorobenzimidazole,5-trifluoromethylbenzimidazole, 5-methoxycarbonyl benzimidazole or5-cyano-6-chlorobenzimidazole ring; and X1, and X3 each represents aniodine, bromine, chlorine, p-toluene sulfonic acid, benzene sulfonicacid, ethyl sulfate, perchlorate, or rhodan ions.
 4. The silver halidephotographic emulsion of claim 1, wherein said dye of the generalformula (I) is
 5. The silver halide photographic emulsion of claim 1,wherein said dyes of the general formula (I), and (III) are present at alevel of from about 5 X 10 3 to 1 X 10 6 mol of dye per mol of silverand wherein the molar ratio of the amount of dye of the general formula(II) and (III) to the amount of dye of the general formula (I) is about1:100 to 1:1.
 6. The silver halide photographic emulsion of claim 1,wherein Z1 is a Beta -naphthothiazole ring, Z2 is a benzoxazole ringwhich is suBstituted at the 5-position with a chlorine atom, atrifluoromethyl group, a methyl group or a phenyl group and A1 is anethyl group.
 7. The silver halide photographic emulsion of claim 1,wherein A3 is a hydrogen atom, a methyl group, or an ethyl group, R5 andR6 each is a methyl group, an ethyl group, a propyl group, an allylgroup, a carboxyalkyl group, or a sulfoalkyl group.
 8. The silver halidephotographic emulsion of claim 1, wherein said emulsion additionallycontains phenol or naphol series cyan coupler.
 9. A silver halidephotographic material comprising a support having thereon the silverhalide emulsion of claim 1.